Condensation reaction



Patented July UNITED STATES, PATEN T OFFICE- coNnnNsArIoN REACTION Donald John Loder, Wilmington, Del., assignor to incurs a Company, Wilmington, Del., a corporation oi Delaware No Drawing Original application October 26,

E. I. du Pont de Ne 1935, Serial No. cation January 6.

1939, Serial No. 249,592

Divided and this appli Claims. (01. 260-338) This invention relates'to anew catalyst for organic synthesis and more particularly to boron halide catalysts. .The application is a division of U. S. Patent 2,158,031 issued May'16, 1939.

In the Friedel-Crafts reactions for the synthesis of aromatic hydrocarbons, ketones and triphenyl methane derivatives, anhydrous aluminum chloride or an analogous anhydrous halide such as boron fluoride, have been used as the condensing agents. These agents are used in comparatively large proportions as they form,

'in such reactions, well-defined addition compounds which are in many reactions considered prepared from boron-halogen containing compounds. A further object of the invention is to provide a new and improved class of condensing agents particularly for reactions requiring an acid type condensing agent, such, for example, as: the interaction ofolefines and carbon monoxide to produce acids and esters, the interaction of organic acids with olefines to providehigh molecular weight esters, and many of the reactions of the Friedel-Crafts type. A still further object of the invention is to provide hydrated boron halide catalysts for accelerating organic reactions of the above types. Other obj'e ts and advantages of the invention will hereina ter appear.

I have found that organic reactions such as the preparation of organic acids and their esters by the interaction of carbon monoxide with olefines and reactants which decompose to form such compounds, as well as the Friedel-Crafts type of reactions in which water is not detrimental, can be catalyzed with certain hydrated boron trihalides. These catalysts are particularly effective in reactions requiring superatmospheric pressures. They are also well fittedfor catalyzing generally such organic condensation reactions in which water is not detrimentaland which require an acidic type catalyst; they are especially adapted for reactions in which an olefine is one of the reactants. A few of the I reactions for which these catalysts are suitable include: i

omoaomom 11.013.011.12: (I) CHRs RzCH. V RCOOH+olefineester Benzene+olefinealkyl benzene Phenol+olefinephenol ether and/or substituted phenol Phenol+RCOOH-phenyl alkyl ketone In the above reactions R indicates an alkyl, aryl or aralkyl grouping.

My preferred condensing agents for reactions such as those illustrated above and their equivalents are the boron trihalides associated with water in the ratio ranging preferably from one to five moles per mole of boron trihalide. More specifically they include the boron trihalides associated with water as a mono-, di-, ,triand quatri-hydrate. of the trifluoride, tribromide, or triiodide of boron. Furthermore, as the boron trihalides form intermediate products which may be designated as intermediate hydratesbetween those definitely stated above, it is understood a that such hydrates are likewise suitable as condensing agents.

It has been stated heretofore that the principal difllculty encountered in the use of anhydrous halides, and more particularly aluminum halide, arose from the necessary destruction of the condensing agent prior to the. recovery of the'products of the reaction. An additional difliculty, in the use of such agents is encountered in handling the anhydrous agents and maintaining them in the anhydrous form. The condensing agents of the present invention can be readily separated by distillation, extraction, decantation or by other means from the reaction products and the recovered agents, generally without the necessity of purification, can be reused directly to accelerate another reaction.

The striking advantages of these recoverable.

highly reactive condensing agents over the anhydrous condensing agents are self evident.

Generally the condensing agents .may be prepared by reacting a liquid halogen acid with a boric acid. For example, three moles of liquid hydrofluoric acid may be reacted with one mole of solid orthoboric acid to give the liquid trithree moles of metaboric acid to give ,the dihy-' drate of boron trifluoride.

I shall now describe more specifically methods of preparing the condensing agent of the invention and also processes in which they may be used but it will be understood that the details thereingiven will not limit the scope of the invention.

Example 1.--1696 parts by weight of solid orthoboric acid are placed in a suitable pressure sustaining receptacle and 1643 parts by weight of liquid hydrofluoric acid are added thereto. The temperature of the exothermic reaction is kept at approximately C., and when the reaction of the hydrofluoric acid with the boric acid is complete a liquid, fairly mobile trihydrate of boron trifluoride, having a specific gravity of 1.500. at C., is obtained.

Example 21-468 parts by weight of liquid hydrofluoric acid are combined as in Example 1 with 175 parts by weight of metaboric acid. The liquid catalyst obtained is apparently a dihydrate of boron trlfluoride having a specific gravity of 1.625 at 20 C.

As has already been emphasized the condensing agents of the present invention may be utilized in a number of reactions and are most ad vantageously employed in condensation reactions in which water is not detrimental. I shall now give an example illustrating the type of process in which my preferred condensing agents may be employed, but the utility of the catalysts is not limited by or to the process.

Example 3.Formalin, 172 parts by weight, was caused to absorb 150 parts of boron fluoride gas. The resulting mixture absorbed propylene at from 0 C.-20 C., and one atmosphere pressure, forming a product which, when madealkaline, and distilled, yielded a series of formals.

by weight and 123 C. to 250 C., was 15 parts by weight.

My condensing agents may be used in various proportions which are governed by the type of reaction. In the absence of addition agents such as metal oxides or powdered metals, for example,

nickel and nickel oxides, they may be used in The lower boiling products (distilling at 30 to proportions ranging from 0.25 to 2.0 mol or higher calculated on the boron halide present per mol of the major reactant while in the presence of addition agents much lower amounts may be employed, say, generally, from 1 to 5% and, in some instances, higher percentages may be re quired. The activity of the addition agent de- .termines in large measure theamount required, the particular reaction as well as the temperature and pressure conditions employed also being considered.

From a consideration of the above specification it will be realized that many changes may be made in the catalysts herein described and the method of their preparation without departing from the invention or sacrificing any of the advantages that may be derived therefrom.

I claim:

1. A process for the preparation of high-boiling formals which comprises reacting a formalin solution with propylene in the presence of hydrated boron fluoride as the catalyst and recovering the formal from the reaction product.

2. A process for the preparation of high-boiling formals which comprises reacting 172 parts of formalin with propylene in the presence of parts of boron trifluoride, at a temperature between 0 C. and 20 C., neutralizing the resulting product and recovering the formals from the neutralized product.

3. A process for the preparation of olefine condensation products which comprises reacting an aldehyde with an olefine in the presence of hydrated boron fluoride as the catalyst and subsequently recovering the condensation product from the reaction mixture.

4. In a process involving the reaction of an olefine with an aldehyde, the step which comprises effecting the reaction between the oleflne and the aldehyde in the presence of a liquid water-boron trifluoride catalyst.

5. In a liquid phase process involving the reaction of an olefine with an aldehyde the step which comprises effecting the reaction between the olefine and the aldehyde in the presence of a liquid water-boron trifluoride catalyst containing from 1 to 5 moles of water per mole of boron trifiuoride.

DONALD JOHN LODER.

the yield of products boiling at 

